Bioaccumulation of toxicants in the zebra mussel, Dreissena polymorpha, at the Times Beach Confined Disposal Facility, Buffalo, New York

This study consisted of a site characterization followed by biomonitoring the zebra mussel, Dreissena polymorpha, at the Times Beach Confined Disposal Facility (CDF), located in Buffalo, New York. Concentrations of selected contaminants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and metals -arsenic (As), chromium (Cr), barium (Ba), mercury (Hg), cadmium (Cd), lead (Pb), selenium (Se) and silver (Ag)-were at or below detection limits in the water column. Sediment contaminant concentrations, recorded as dry weight, were as high as 549 mg/kg for total PAHs, 9 mg/kg for PCB Aroclor 1248 and 54, 99, 6, 355, 637 and 16 mg/kg for the metals As, Ba, Cd, Cr, Pb and Hg, respectively. To predict contaminant bioavailability, elutriate and whole sediment toxicity tests were performed utilizing the cladoceran, Daphnia magna. Whole sediment tests indicated significant impact. Control survival was 84%, while sediment treatment had survival ranging from 1 to 7%. Mean control reproduction was 86.8 neonates, whereas treatment reproduction ranged from 1.4 to 9.0. Zebra mussels placed both in the water column (Upper) and at the sediment level (Lower) survived the 34-day exposure. Contaminants that significantly accumulated in zebra mussel tissue (wet wt mg/kg) were total PAHs (6.58), fluoranthene (1.23), pyrene (1.08), chrysene (0.98), benzo(a)anthracene (0.60), PCB Aroclor 1248 (1.64), As (0.97), Cr (2.87) and Ba (7.00). Accumulation of these contaminants in zebra mussel tissue represent a potentially realistic hazard to organisms (i.e. fish and birds) that feed on them.     

Influence of particle characteristics and organic matter content on the bioavailability and bioaccumulation of pyrene by clams

Hydrophobic chemicals are known to associate with sediment particles including those from both suspended particulate matter and bottom deposits. The complex and variable composition of natural particles makes it very difficult therefore, to predict the bioavailability of sediment-bound contaminants. To overcome these problems we have previously devised a test system using artificial particles, with or without humic acids, for use as an experimental model of natural sediments. In the present work we have applied this experimental technique to investigate the bioavailability and bioaccumulation of pyrene by the freshwater fingernail clam Sphaerium corneum. The uptake and accumulation of pyrene in clams exposed to the chemical in the presence of a sample of natural sediment was also investigated. According to the results obtained, particle surface properties and organic matter content are the key factors for assessing the bioavailability and bioaccumulation of pyrene by clams.     

A summary of total mercury concentrations in flora and fauna near common contaminant sources in the Gulf of Mexico

Total mercury concentrations are summarized for environmental media and biota collected from near-coastal areas, several impacted by contaminant sources common to the Gulf of Mexico. Water, sediment, fish, blue crabs, oysters, clams, mussels, periphyton and seagrasses were collected during 1993–2002 from targeted areas affected by point and non-point source contaminants. Mean concentrations in water and sediment were 0.02 (±1 standard deviation = 0.06) μg l⁻¹ and 96.3 (230.8) ng g⁻¹ dry wt, respectively. Mean total mercury concentrations in fish, blue crabs, brackish clams and mussels were significantly greater than those in sediment, seagrass, colonized periphyton and oysters. Concentrations (ng g⁻¹ dry wt) averaged 23.1 (two seagrass species), 220.1 (oysters), 287.8 (colonized periphyton), 604.0 (four species of freshwater mussels), 772.4 (brackish clam), 857.9 (blue crabs) and 933.1 (nine fish species). Spatial, intraspecific and interspecific variability in results limited most generalizations concerning the relative mercury contributions of different stressor types. However, concentrations were significantly greater for some biota collected from areas receiving wastewater discharges and golf course runoff (fish), agricultural runoff (oysters) and urban stormwater runoff (colonized periphyton and sediment). Marine water quality criteria and proposed sediment quality guidelines were exceeded in 1–12% of total samples. At least one seafood consumption guideline, criteria or screening value were exceeded in edible tissues of blue crabs (6% total samples) and nine fish species (8–33% total samples) but all residues were less than the US Federal Drug Administration action limit of 1.0 ppm and the few reported toxic effect concentrations available for the targeted biota.     

The role of algae (Isochrysis galbana) enrichment on the bioaccumulation of benzo[a]pyrene and its effects on the blue mussel Mytilus edulis

The role of algal concentration in the transfer of organic contaminants in a food chain has been studied using the ubiquitous model polycyclic aromatic hydrocarbon benzo[a]pyrene (BaP) as the contaminant, Isochrysis galbana as the phytoplankton food source, and the common mussel (Mytilus edulis) as the primary consumer. The effect of algal concentration on BaP uptake by M. edulis was determined by feeding M. edulis daily with I. galbana which had previously been kept in the presence of BaP for 24 h. Four combinations of concentrations of algae and BaP were used to give final exposure concentrations of 30,000 or 150,000 algal cells ml(-1) in combination with either 2 or 50 microg BaP l(-1). BaP concentrations were determined fluorometrically in rest tissues (excluding digestive glands) and digestive gland microsomal fractions of M. edulis after 1, 7 and 15 days exposure, and also in isolated algae. Potentially toxic effects of BaP on M. edulis were examined in terms of blood cell lysosomal membrane damage (neutral red dye retention assay) and induction of digestive gland microsomal mixed-function oxygenase (MFO) parameters [BaP hydroxylase (BPH) and NADPH-cytochrome c (P450) reductase activities]. BaP bioaccumulation in rest tissues (and to a lesser extent in digestive gland microsomes) of M. edulis increased with both increasing BaP and algal exposure concentrations, and over time, producing maximal bioconcentration factors in rest tissues after 15 days exposure to 150,000 algal cells ml(-1) and 50 microg BaP l(-1) of 250,000. The five-fold higher concentration of algae increased BaP bioaccumulation by a factor of approximately 2 for 50 microg BaP l(-1) at day 15. Blood cell neutral red dye retention time decreased linearly with increasing log(10) tissue BaP body burden, indicating an increased biological impact on M. edulis with increasing BaP exposure possibly due to a direct effect of BaP on blood cell lysosomal membrane integrity. An increase was seen in NADPH-cytochrome c reductase activity, and indicated in BPH activity, with 1 but not 7 or 15 days exposure to BaP, indicating a transient response of the digestive gland microsomal MFO system to BaP exposure.     

Bioaccumulation of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene by mussels transplanted in a coastal lagoon

The bioaccumulation of two isomeric non-alternant non-priority polycyclic aromatic hydrocarbons (PAHs), namely cyclopenta[cd]pyrene and benzo[ghi]fluoranthene, was investigated in caged mussels (Mytilus galloprovincialis) exposed for 30 days in three sites of a coastal lagoon (Pialassa Baiona, Ravenna, Italy) contaminated by pyrogenic PAHs. The concentration of cyclopenta[cd]pyrene and benzo[ghi]fluoranthene increased from undetectable levels in reference mussels withdrawn from the Adriatic sea to 10-30 ng g(-1) dry weight in transplanted mussels. Other contaminants bioaccumulated by caged mussels included pyrene, fluoranthene and mercury. Whilst the isomer concentration ratio pyrene/fluoranthene in biota was comparable to that observed in sediments, the cyclopenta[cd]pyrene/benzo[ghi]fluoranthene ratio was much lower in mussels than in sediments. The lower sediment biota accumulation factor of cyclopenta[cd]pyrene with respect to that of benzo[ghi]fluoranthene was tentatively attributed to the greater biological activity of the former compound, which contains a reactive olefinic bond in the cyclopenta fused ring moiety. Given the higher mutagenic activity of cyclopenta[cd]pyrene with respect to other priority PAHs, its bioaccumulation from contaminated sediments may rise considerably the overall toxicity of PAH residues in exposed biota.     

Comparisons of coarse and fine versions of two carbons for reducing the bioavailabilities of sediment-bound hydrophobic organic contaminants

Coarse (whole) and finely ground Ambersorb 1500 and coarse and fine coconut charcoal were compared as to their efficiencies in scavenging organic contaminants desorbed from sediment. Aqueous slurries of a test sediment spiked (1 ppm) with p,p^′-DDE (DDE), 2,2^′,5,5^′-tetrachlorobiphenyl (TCB), naphthalene (NAP), or phenanthrene (PHEN), and containing 1% levels of the test carbons were treated by shaking at 35 °C while exposed to clusters of low-density polyethylene membrane (detox spiders). Controls consisted of spiked sediments and detox spiders but no added carbon of any kind and thus represented unimpeded bioavailabilities (to the spiders). After the treatments––agitation periods from 2.5 to 60 h, depending on contaminant hydrophobicity––the exposed detox spiders were analyzed. The fine carbon of either type was more effective than its coarser variant in obstructing contaminant bioavailabilities. The finer variants of both carbons obstructed the bioavailabilities of NAP and PHEN equally well as did the coarser variants of both. Whole Ambersorb 1500 and coarse coconut charcoal were similarly ineffective in intercepting TCB and DDE. Ground Ambersorb 1500 obstructed virtually all bioavailability of all four contaminants and was far more effective than fine coconut charcoal in intercepting DDE and TCB. An additional experiment compared the effectiveness of ground Ambersorb 1500 and fine coconut charcoal in obstructing the bioavailabilities from sediment of a broad array of spiked organochlorine pesticides. The performance of ground Ambersorb 1500 was again found to be superior; the bioavailable levels of each of the 27 pesticides were markedly lower in the presence of ground Ambersorb 1500 than in the presence of fine coconut charcoal.     

Trends in spatial and temporal levels of persistent organic pollutants in Lake Erie sediments

A Lake Erie sediment survey was conducted in 1997 to characterize spatial trends in contamination, and for comparison with a 1971 survey to assess any changes in environmental quality since the advent of measures to reduce contaminant sources. Contaminant data for some contaminant classes in 1971 was based on analysis of frozen archived samples, thereby allowing a direct comparison between surficial sediment contamination in 1971 and 1997 based on modern analytical methods. Lake-wide contaminant concentrations of polychlorinated biphenyls (PCBs) and organochlorine compounds including hexachlorobenzene and the DDT compounds in 1997 were substantially lower, compared to levels in samples collected in 1971. Lake-wide average sediment PCB levels were found to have decreased roughly 70% from 136 ng/g in 1971 to 43 ng/g in 1997. Similarly, reductions in other compound classes ranged from 40% to 80%. In 1997, some individual contaminants classes including PCBs exhibited a spatial trend toward increasing sediment contamination from the eastern basin to the western basin, and from the north-central basin to the south-central basin. Levels of organic contaminants in sediments in some areas of Lake Erie still exceeded the strictest Canadian Federal and Ontario Provincial guidelines. However, exceedances of guidelines describing contaminated environments in 1997 were predominantly restricted to the western basin and near-shore sites in the southern part of the central basin.     

Chemical and biological profiles of sediments as indicators of sources of genotoxic contamination in Hamilton Harbour. Part I: analysis of polycyclic aromatic hydrocarbons and thia-arene compounds

Bottom sediment and suspended sediment samples from Hamilton Harbour (western Lake Ontario) and from a major tributary were profiled using polycyclic aromatic hydrocarbons (PAH) and thia-arenes as source apportionment tracers. Ratios of selected PAH and ratios of monomethyl and dimethyl/ethyl dibenzothiophenes to the parent dibenzothiophenes were calculated. Thia-arene and PAH profiles of Standard Reference Material SRM 1649 (urban dust/organics), SRM 1650 (diesel), SRM 1597 (coal tar), Hamilton coal tar and a composite Hamilton air particulate sample provided source sample data. The gas chromatography-mass spectrometry (GC-MS) chromatograms of all sample extracts were dominated by homocyclic PAH but interpretation of PAH profiles with respect to source was difficult. In contrast, thia-arene analyses revealed more distinct differences in profiles of samples collected in different areas of the harbour, including the tributary. These results indicated that areas of coal tar-contaminated sediment are potential contributors to the overall contaminant burden of sediments and suspended sediments in Hamilton Harbour. These data also indicated that contaminants related to mobile combustion sources were entering the harbour via a major tributary.     

Volatilization of contaminants from suspended sediment in a water column during dredging

Remedial dredging of contaminated bed sediments in rivers and lakes results in the suspension of sediment solids in the water column, which can potentially be a source for evaporation of hydrophobic organic compounds (HOCs) associated with the sediment solids. Laboratory experiments were conducted in an oscillating grid chamber to simulate the suspension of contaminated sediments and flux to air from the surface of the water column. A contaminated field sediment from Indiana Harbor Canal (IHC) and a laboratory-inoculated University Lake (UL) sediment, Baton Rouge, LA, were used in the experiments, where water and solids concentration and particle size distribution were measured in addition to contaminant fluxes to air. A transient model that takes into account contaminant desorption from sediment to water and evaporation from the water column was used to simulate water and sediment concentrations and air fluxes from the solids suspension. In experiments with both sediments, the total suspended solids (TSS) concentration and the average particle diameter of the suspended solids decreased with time. As expected, the evaporative losses were higher for compounds with higher vapor pressure and lower hydrophobicity. For the laboratory-inoculated sediment (UL), the water concentrations and air fluxes were high initially and decreased steadily implying that contaminant release to the water column from the suspended solids was rapid, followed by evaporative decay. For the field sediments (IHC), the fluxes and water concentrations increased initially and subsequently decreased steadily. This implied that the initial desorption to water was slow and that perhaps the presence of oil and grease and aging influenced the contaminant release. Comparison of the model and experimental data suggested that a realistic determination of the TSS concentration that can be input into the model was the most critical parameter for predicting air emission rates.     

Comparative study of immobilized Trametes versicolor laccase on nanoparticles and kaolinite

Laccase from Trametes versicolor was immobilized on nanoparticles and kaolinite by physical adsorption or chemical covalence in which the supporters were activated by cross-linked with glutaraldehyde. Thermal and pH stabilities of immobilized laccase on these different supporters were compared. The degradation efficiencies of these immobilized laccases on oxidation of benzo[a]pyrene (BaP) were also compared. The results showed that the immobilized laccases on nanoparticles were more stable in resisting pH and thermal changes. After 48h oxidation, laccase immobilized on kaolinite using the covalent coupling method showed a higher efficiency of oxidation with the BaP residue of 23% in the presence of 1mM HBT and with BaP residue of 37% in 1mM ABTS as the mediator. The results also exhibited a significant inhibition by 1% surfactant Tween 80. According to the HPLC analysis, the oxidation products including 1,6-benzo[a]pyrene quinone, 3,6-benzo[a]pyrene quinone and 6,12-benzo[a]pyrene quinone were identified.     

Comparative distribution, sourcing, and chemical behavior of PCDD/Fs and PCBs in an estuary environment

PCDD/F and PCB field data (1041 samples) in five media (dissolved, suspended sediment, bed sediment, catfish, and blue crab) were studied to explore dual contaminant patterns in the Houston Ship Channel, Texas, USA. PCDD/Fs showed greater concentration than PCBs in suspended sediments while PCBs were higher in apparent dissolved (truly dissolved + DOC-associated), fish, and crab. PCDD/Fs at nearly all locations contributed more strongly to dioxin-like toxicity. The fraction of PCB TEQ was, however, enriched in biotic over abiotic media due in large part to the presence of PCB 126, which was mostly undetected in water and sediment and yet exhibited a BAF three times greater than 2,3,7,8-TCDD. Dissolved-suspended sediment and suspended-bed sediment relationships showed that (1) observed apparent dissolved concentration differences (as fraction of total water were mean 10% PCDD/Fs and 63% PCBs) can reasonably be explained by a four-phase partition model (truly dissolved, DOC-associated, suspended OC, and suspended BC) for PCBs but not for PCDD/Fs and (2) the contaminants behaved similarly in bed to suspended sediment concentration ratios (C_bed/C_susp) upstream of a major confluence but not downstream. PCA-cluster analysis pointed to the possibility that suspended sediment PCB contamination originates from resuspended bed sediment while PCDD/Fs in suspended sediment originates more probably from other sediment sources such as upstream wash load or air deposition. Finally, examinations of a congener marker ratio (PCB 209/206) seemed to indicate that a source of pure PCB 209 may exist in bed sediment near Patrick Bayou though the source was not completely localized.     

Polycyclic aromatic hydrocarbons in sediments,pore water and the amphipod Pontoporeia hoyi from Lake Michigan

Polycyclic aromatic hydrocarbon (PAH) concentrations were measured in Pontoporeia hoyi, the most abundant benthic organism in Lake Michigan, and in its associated sediment/pore water matrix. Individual PAH concentrations ranged from 10 ppb to 1 ppm in three sedimentary environments having different levels of organic carbon. Pore water concentrations appeared to be independent of sediment concentrations. P. hoyi bioconcentration factors ranged from approximately 10⁴ to 10⁵ for seven analyzed PAHs. A major fraction of the phenanthrene, fluoranthene and pyrene in P. hoyi appears to come from sediments and pore water, while chrysene and BaP are primarily obtained from water.     

Bioaccumulation of butyltins in Dreissena polymorpha at a confined placement facility in Buffalo, New York

This study involves a site characterization followed by biomonitoring with the zebra mussel, Dreissena polymorpha, at the Times Beach confined placement facility (CPF), located in Buffalo, NY. The contaminant of interest was tributyltin (TBT) and the degradation products dibutyltin (DBT) and monobutyltin (MBT). At study initiation (Day 0) TBT levels in the baseline mussels were 5.86 +/- 0.43 ng Sn/g, DBT levels were 2.25 +/- 0.37 ng Sn/g. No MBT was detected in the Day 0 baseline samples. Caged reference mussels placed back in the Black Rock Channel Lock and retrieved on Days 19 and 34 had TBT, DBT, and MBT levels which did not differ significantly from the Day 0 baseline levels. Mussels placed at the Times Beach CPF had TBT concentrations that were significantly lower at both Days 19 (3.65 +/- 0.90 ng Sn/g) and 34 (3.50 +/- 1.03 ng Sn/g) than the Day 0 baseline analysis (5.86 +/- 0.43 ng Sn/g). The results of this study indicate that butyltins were detected at the CPF site in the sediment (7.33 +/- 5.70 ng Sn/g) but not the water column (not detected at 0.01 microgram/l). In this study the zebra mussel was able to depurate TBT even in the presence of contaminated sediment. TBT may be bioaccumulated from the sediments. However, the initial levels in the mussels were so high, levels actually dropped as sediment-tissue equilibria levels were reached by the mussels.     

Impact of dredged urban river sediment on a Saronikos Gulf dumping site (Eastern Mediterranean): sediment toxicity,contaminant levels,and biomarkers in caged mussels

Impacts of chemical contaminants associated with dumping of dredged urban river sediments at a coastal disposal area in Saronikos Gulf (Eastern Mediterranean) were investigated through a combined approach of sediment toxicity testing and active biomonitoring with caged mussels. Chemical analyses of aliphatic hydrocarbons (AHs), polycyclic aromatic hydrocarbons (PAHs), Cu, and Zn in combination with the solid phase Microtox® test were performed on sediments. Concentrations of PAHs, AHs, Cu, and Zn as well as multiple biomarkers of contaminant exposure and/or effects were measured in caged mussels. Sediments in the disposal and neighboring area showed elevated PAHs and AHs concentrations and were characterized as toxic by the solid-phase Microtox® test during and after dumping operations. Biomarker results in the caged mussels indicated sublethal effects mainly during dumping operations, concomitantly with high concentrations of PAHs and AHs in the caged mussel tissues. Cu and Zn concentrations in sediments and caged mussels were generally not elevated except for sediments at the site in the disposal area that received the major amount of dredges. High PAHs and AHs levels as well as sublethal effects in the caged mussels were not persistent after termination of operations. The combined bioassay–biomarker approach proved useful for detecting toxicological impacts of dredged river sediment disposal in sediments and the water column. Nevertheless, further research is needed to evaluate whether sediment toxicity will have long-term effects on benthic communities of the disposal area.     

Porous organoclay composite for the sorption of polycyclic aromatic hydrocarbons and pentachlorophenol from groundwater

Complex mixtures of hazardous chemicals such as polycyclic aromatic hydrocarbons (PAHs) in contaminated soil and groundwater can have severe and long-lasting effects on health. The evidence that these contaminants can cause adverse health effects in animals and humans is rapidly expanding. The frequent and wide-spread occurrence of PAHs in groundwater makes appropriate intervention strategies for their remediation highly desirable. The core objective of this research was to assess the ability of a clay-based composite to sorb and remove toxic contaminants from groundwater at a wood-preserving chemical waste site. Treatment efficiencies were evaluated using either effluent from an oil-water separator (OWS) or a bioreactor (B2). The effluent water from these units was passed through fixed bed columns containing either an organoclay composite or granular activated carbon. The sorbent columns were placed in-line using existing sampling ports at the effluent of the OWS or B2. Individual one-liter samples of treated and untreated effluent were collected in Kimax bottles over the course of 78 h (total of 50 samples). Subsequently each sample was extracted by solid phase extraction methodology, and pentachlorophenol (PCP) and PAH concentrations were quantitated via GC/MS. Columns containing porous organoclay composite, i.e. sand-immobilized cetylpyridinium-exchanged low-pH montmorillonite clay (CP/LPHM), were shown to reduce the contaminant load from the OWS effluent stream by 97%. The concentrations of benzo[a]pyrene (BaP) and PCP were considerably reduced (i.e. >99%). An effluent stream from the bioreactor was also filtered through columns packed with composite or an equivalent amount of GAC. Although the composite reduced the majority of contaminants (including BaP and PCP), it was less effective in diminishing the levels of lower ring versus higher ring PAHs. Conversely, GAC was more effective in removing the lower ring PAHs, except for naphthalene and PCP. The effectiveness of sorption of PCP from the OWS effluent by the composite was confirmed using a PCP-sensitive adult hydra bioassay previously described in our laboratory. The findings of this initial study have delineated differences between CP/LPHM and GAC for groundwater remediation, and suggest that GAC (instead of sand) as the solid support for organoclay may be more effective for the treatment of contaminated groundwater under field conditions than GAC or CP/LPHM alone. Further work is ongoing to confirm this conclusion.     

Elevated in-home sediment contaminant concentrations - the consequence of a particle settling-winnowing process from Hurricane Katrina floodwaters

Sediment samples were collected from two homes which were flooded in the wake of Hurricane Katrina in August 2005. The samples were analyzed for trace metals and semi-volatile organic compounds using techniques based on established EPA methods. The data showed higher concentrations of some metals and semi-volatile organic pollutants than reported in previous outdoor sampling events of soils and sediments. The Lake Pontchartrain sediments became resuspended during the hurricane, and this material subsequently was found in the residential areas of New Orleans following levee breaches. The clay and silt particles appear to be selectively deposited inside homes, and sediment contaminant concentrations are usually greatest within this fraction. Re-entry advisories based on outdoor sample concentration results may have under-predicted the exposure levels to homeowners and first responders. All contaminants found in the sediment sampled in this study have their origin in the sediments of Lake Pontchartrain and other localized sources.     

Persistent organic pollutants in Detroit River suspended sediments: polychlorinated dibenzo-p-dioxins and dibenzofurans,dioxin-like polychlorinated biphenyls and polychlorinated naphthalenes

Suspended sediments from the Detroit River were collected in 1999 and 2000 using sediment traps at sites ranging from western Lake Erie to southern Lake St. Clair and analyzed to determine the spatial distributions of contaminants including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), dioxin-like PCBs (DLPCBs) and polychlorinated naphthalenes (PCNs). Concentrations of all three contaminant classes were clearly elevated at sites in the lower reaches of the river in the Trenton Channel. The potential influence of the Trenton Channel as a source of contamination to western Lake Erie was further evidenced by PCDD/PCDF homologue profiles, which indicated a contribution from chemical manufacturing in addition to the normal background combustion profile. Toxic equivalents (TEQs) for PCDDs/PCDFs generally exceeded those for DLPCBs; combined total TEQs in July 2000 for these two compound classes ranged from 2.30 pg/g in southern Lake St. Clair to 306 pg/g at a station just downstream of the outflow of Monguagon Creek in the Trenton Channel. The spatial distribution of PCN contamination was similar to that of PCDDs/PCDFs and DLPCBs, with the highest level of total PCNs (8200 ng/g) detected at a site in the Trenton Channel near Elizabeth Park; TEQs for PCNs in the Trenton Channel ranged from 73 to 3300 pg/g. The data indicate that PCNs represent a significant contribution to dioxin-like biological activity in Detroit River suspended sediments.     

Nitro-PAH formation studied by interacting artificially PAH-coated soot aerosol with NO2 in the temperature range of 295–523 K

Diesel particulate matter poses a threat to human health, and in particular nitrated polycyclic aromatic hydrocarbons (NPAHs) found within and on the surface of these particles. Although diesel particulate filters (DPFs) have been designed and implemented to reduce these and other harmful diesel emissions, the particle loaded filters may act as a reaction chamber for the enhanced production of NPAHs from the nitration of PAHs with NO₂.Focus is on the investigation of the heterogeneous reactions that occur on soot particles by exposing laboratory produced pyrene- or benzo(a)pyrene-coated spark discharge soot particles to varying concentrations of NO₂ and temperatures while following the formation of products over time. The sole nitration product that was observed throughout the experiments with pyrene-coated soot was 1-nitropyrene (1-NPYR), which increased linearly with reaction time for all NO₂ concentrations chosen (0.11, 1.0, 2.0, 4.0 ppm, m m^?1). Resulting 1-NPYR formation rate increased exponentially with [NO₂]. Throughout the 3-h experiments less than 10% of pyrene has been converted to 1-NPYR and the partial reaction order with regard to [NO₂] was estimated to 1.52. Benzo(a)pyrene (BaP) was more reactive than pyrene. After 3 h reaction time almost 80% of the BaP has been converted to 6-NBaP.Highest 1-NPYR concentrations on particles were detected at 373 K, and at higher temperatures a considerable decrease in particulate 1-NPYR was observed. A similar trend was observed in a DPF simulation system (PM-Kat^®-like) with BaP-coated soot. In this case, highest 6-NBaP concentration on particles was detected at 423 K. Backed by corroborating results from separate gas/solid-phase partition experiments with 1-NPYR and 6-NBaP, it is likely that the newly formed 1-NPYR and 6-NBaP became transferred from particle to gas phase at higher temperatures. Results from this study confirm the presence of 1-NPYR and 6-NBaP in particulate and gas phase under conditions encountered in DPFs, especially when operated at low temperature situations of the aftertreatment system.     

Pyrene bioavailability; effect of sediment-chemical contact time on routes of uptake in an oligochaete worm

Bioavailability of sediment-sorbed compounds may vary with increasing contact time. This may result in the dietary uptake route becoming more significant as conditions in the gut flora aid the extraction of contaminants, which have migrated into sites within the sediment particle. Such mechanisms may have important implications on risk assessments performed on substances released into the environment. A series of experiments were carried out using sediment spiked with 14C-labelled pyrene, a polycyclic aromatic hydrocarbon. The sediment was left at room temperature over a period of 220 days. Periodically (at 0, 1, 14, 28, 70, 220 days) the sediment was used to perform a bioaccumulation study using the freshwater oligochaete Lumbriculus variegatus. A novel methodology using feeding and (decapitated) non-feeding worms, allowed differentiation between uptake via ingestion and simple sorption. Results showed that there was a decline in bioavailability with time and that this was a 3 stage process. A rapid initial decline was observed over the first day when a 40% decrease was measured, an intermediate period were levels remained stable (day 14 to day 70) and an ultimate decrease in pyrene activity in worm tissue of 70% after 220 days. Over this period the chemical extractability of pyrene also decreased by 50%, as the chemical migrated deeper into unavailable sites within the sediment matrix. Normalising bioavailability to the chemically extractable fraction of pyrene within the sediment provided an overall decrease in bioavailability of 58%. The importance of the dietary route of uptake for pyrene varied during the sediment aging process, reflecting the changes in the physico-chemical interactions between the pyrene, sediment and pore water.     

Distribution characteristics of nonylphenols in the artificial Lake Shihwa, and surrounding creeks in Korea

Nonylphenols were determined from the water, suspended particle, and sediment samples taken from the Lake Shihwa in Korea and its surrounding creeks flowing through municipal and industrial areas, and into the lake. The nonylphenols were detected at the concentration ranges of 0.0-41.3 microg/l, 0.0-116.6 and 0.3-31.7 mg/kg in water, suspended particle and sediment samples respectively. The contamination levels of nonylphenols were increased along the down stream. Considerably high levels of nonylphenols were found at the industrial area compared to the municipal area. No remarkable differences were found between the isomer patterns of nonylphenols for the sample matrices of each sampling site, i.e. water, suspended solids and sediment. Strong correlations between water and sediment with 10(5.2) of the mean partition coefficient (Koc ) were observed. These indicate that most of nonylphenols came from industrial wastewater at high level. It is thought that the water quality of the Lake Shihwa is affected greatly by industrial environments surrounding.